Silicone solvents for antiperspirant salts

ABSTRACT

Silicone compositions that are functionalized with 1,2 or 1,3 glycol bearing substituents render antiperspirant salts soluble, partially soluble therein or partially miscible therewith. Such functionalized silicones in conjunction with antiperspirant salts produce clear antiperspirant gel sticks.

FIELD OF THE INVENTION

The present invention relates to new silicone compositions that arefunctionalized wherein antiperspirant salts are rendered partiallysoluble therein or are rendered partially miscible therewith.

BACKGROUND OF THE INVENTION

Enhanced efficacy aluminum and aluminum-zirconium antiperspirant saltsare well known and are described, for example, U.S. Pat. No. 4,359,456;U.S. Pat. No. 4,775,528; U.S. Pat. No. 4,859,446, U.S. Pat. No.4,871,525; U.S. Pat. No. 4,900,534; U.S. Pat. No. 4,944,933; U.S. Pat.No. 5,202,115; U.S. Pat. No. 5,234,677; U.S. Pat. No. 5,296,623; andU.S. Pat. No. 5,330,751. These enhanced salts are also known to rapidlyrevert back to their non-enhanced state in solution, particularly atconcentrations greater than 20%. Consequently, the enhancedantiperspirant salts are generally only available in powder form.

A number of references describe various ways of making alcohol solubleantiperspirant actives. These references include, for example, U.S. Pat.No. 3,405,153; U.S. Pat. No. 3,420,932; U.S. Pat. No. 3,523,130; andU.S. Pat. No. 3,947,556. In each case concentrated solutions of theantiperspirant active (i.e., in the 40 to 50% range) are employed as astarting material and the product is obtained as a powder, which mustthen be redissolved in the desired alcohol solution. Such techniquespre-date the availability of enhanced efficacy salts and are notbelieved to be applicable thereto as they would likely cause reversionto the non-enhanced state. An alcohol soluble complex of aluminumchlorohydrate and propylene glycol may be prepared by spray drying apropylene glycol solution of the aluminum chlorohydrate.

Two methods of making polyhydric alcohol solutions of antiperspirantsalts have been described. In one method a powdered antiperspirant salt,which may be an enhanced efficacy salt, is dissolved directly in apolyhydric alcohol, such as propylene glycol. In the other case, thepolyhydric alcohol contains about 10 to 20% water and the antiperspirantsalt has a water content greater than 10%.

A method of making polyhydric alcohol solutions of antiperspirant saltswhich are free of unbound water is described in U.S. Pat. No. 4,781,917.In that method, a powdered antiperspirant salt, which may be an enhancedefficacy salt, is dissolved in water (a 50% solution is exemplified), apolyhydric alcohol, such as propylene glycol, is added to the aqueoussolution, then all of the water is removed by heating under vacuum. Amethod of making a propylene glycol solution of an aluminum-zirconiumantiperspirant salt neutralized with zinc glycinate has also beendescribed. An aqueous solution of aluminum chlorohydrate is refluxed inthe presence of a small amount of propylene glycol, the solution iscooled to 70° C., zirconyl hydroxychloride-gly is added, the solution iscooled to 40° C., then zinc glycinate followed by propylene glycol isadded. This solution is then distilled under vacuum to remove water,leaving a 30% by weight solution of antiperspirant active in propyleneglycol.

The above-described methods suffer from a number of deficiencies. First,many of them are not efficient because they utilize a powdered material.Isolation of a powdered antiperspirant salt from solution is timeconsuming and costly. Second, it is believed that these methods willlikely result in some loss of efficacy and/or will not provide clearsolutions. Antiperspirant salts which have been obtained by spray dryingare notoriously difficult to redissolve as clear solutions. Moreover,any method which requires an aqueous salt concentration over 20% willlikely suffer some loss in efficacy.

SUMMARY OF THE INVENTION

I now disclose that by means of a new silicone composition,antiperspirant salts may be dissolved or dispersed in the silicone ofthe present invention and cosmetic, deodorant, antiperspirant, orpersonal care compositions may be formulated therewith. This newsilicone composition enables the formulation of antiperspirant saltcontaining cosmetic, deodorant, antiperspirant, or personal carecompositions that are transparent.

Thus the present invention provides for a silicone compound having theformula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,subject to the limitation that the sum of the subscripts b, d and f isone or greater; where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript h is 1, 2or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript i is 1 or2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is a monovalent hydrocarbon radical selected from the groupconsisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ -- and (HOCH₂)₂ C(CH₂CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formula SiO_(4/2).

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a silicone composition having theformula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,subject to the limitation that the sum of the subscripts b, d and f isone or greater or alternatively the subscript b is a positive integer of2 or greater and the subscript c is a positive integer of 1 or greater;where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript h is 1, 2or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript i is 1 or2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is a monovalent hydrocarbon radical selected from the groupconsisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ -- and (HOCH₂)₂ C(CH₂CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formula SiO_(4/2). The presentinvention also comprises the silicone composition of the presentinvention and a salt of aluminum or zirconium. More particularly thepresent invention is a cosmetic, deodorant, antiperspirant, or personalcare composition that comprises the silicone composition of the presentinvention and a salt of aluminum or zirconium.

The compositions of the present invention are prepared by thehydrosilylation of an organohydrogen silicone having the formula:

    M.sub.a M.sup.H.sub.b D.sub.c D.sup.H.sub.d T.sub.e T.sup.H.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,subject to the limitation that the sum of the subscripts b, d and f isone or greater or alternatively the subscript b is a positive integer of2 or greater and the subscript c is a positive integer of 1 or greater;where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R' is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M^(H) has the formula:

    R.sup.2.sub.3-h H.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D^(H) has the formula:

    H.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T^(H) has the formula:

    HSiO.sub.3/2 ;

and Q has the formula SiO_(4/2) in the presence of H₂ (OH)CCH(OH)CH₂OCH₂ CH═CH₂ or (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH═CH₂.

Hydrosilylation is accomplished in the presence of a suitablehydrosilylation catalyst. The catalyst preferred for use with thesecompositions are described in U.S. Pat. Nos. 3,715,334; 3,775,452; and3,814,730 to Karstedt. Additional background concerning the art may befound at J. L. Spier, "Homogeneous Catalysis of Hydrosilation byTransition Metals, in Advances in Organometallic Chemistry, volume 17,pages 407 through 447, F. G. A. Stone and R. West editors, published bythe Academic Press (New York, 1979). Persons skilled in the art caneasily determine an effective amount of platinum catalyst. Generally, aneffective amount ranges from about 0.1 to 50 parts per million of thetotal organopolysiloxane composition.

The organohydrogen silicone compounds that are the precursors to thecompounds of the present invention may be prepared by the processdisclosed in U.S. Pat. No. 5,698,654 herewith specifically incorporatedby reference. The '654 patent discloses a sequential catalysis of thering opening polymerization of cyclic organosiloxanes using a basecatalyst that can be neutralized by a subsequent redistribution andcondensation catalyst such as a Lewis acid catalyst, preferably aphosphonitrilic compound, that permits the rapid synthesis offunctionalized and poly-functionalized silicone copolymers.

It is to be noted that as pure compounds the subscripts describing theorganohydrogen siloxane precursor and the hydrosilylation adduct of thepresent invention are integers as required by the various rules ofchemical stoichiometry. As mixtures of compounds that are described bythese formulas the subscripts will assume non-integral values, for themixtures. The restrictions on the subscripts heretofore described forthe stoichiometric subscripts of these compounds are for the purecompounds, not the mixtures. In a specific embodiment of the presentinvention, a preferred compound is M'_(b) D_(c) where the subscript b is2 and the subscript c ranges from 1 to 30, preferably from 2 to 20, morepreferably from 3 to 10 and most preferably from 3 to 5.

Antiperspirant salts which may be used in the deodorant compositions ofthe present invention include any of the conventional aluminum,zirconium and aluminum-zirconium salts known to be useful inantiperspirant or deodorant compositions. These salts include aluminumhalides and aluminum hydroxy halides (e.g., aluminum chlorohydrate), andmixtures or complexes thereof with zirconyl oxyhalides and zirconylhydroxyhalides (e.g. aluminum-zirconium chlorohydrate). Preferredaluminum salts are those having the general formula:

    Al.sub.2 (OH).sub.6-z X.sub.z

wherein the anion X is Cl, Br, I or NO3, and z is about 0.3 to about 4,preferably about 1 to 2, such that the Al to X mole ratio is about 1:1to 2.1:1. These salts generally have some water of hydration associatedwith them, typically on the order of 1 to 6 moles per mole of salt. Mostpreferably, the aluminum salt is aluminum chlorohydrate (i.e. X is Cl)and z is about 1, such that the aluminum to chlorine mole ratio is about1.9:1 to 2.1:1.

Preferred aluminum-zirconium salts are mixtures or complexes of theabove-described aluminum salts with zirconium salts of the formula:

    ZrO(OH).sub.2-xb Y.sub.b

wherein the anion Y is Cl, Br, I, NO₃, or SO₄, x is about 0.8 to 2, andp is the valence of Y. The zirconium salts also generally have somewater of hydration associated with them, typically on the order of 1 to7 moles per mole of salt. Preferably the zirconium salt is zirconylhydroxychloride of the formula ZrO(OH)_(2-x) Cl_(x) wherein x is about 1to 2, preferably about 1.2 to about 1.9. The preferredaluminum-zirconium salts have an Al:Zr ratio of about 1.7 to about 12.5,most preferably about 2 to about 10, and a metal: (X+Y) ratio of about0.73 to about 2.1, preferably about 0.9 to 1.5. A preferred salt isaluminum-zirconium chlorohydrate (i.e. X and Y are both Cl), which hasan Al:Z ratio of about 2 to about 10 and a metal:Cl ratio of about 0.9to about 2.1. Thus, the term aluminum-zirconium chlorohydrate isintended to include the tri-, tetra-, penta- and octa-chlorohydrateforms. The aluminum-zirconium salt complexes may also contain a neutralamino acid, preferably glycine (Gly), typically with a glycine tozirconium (Gly:Zr) ratio of about 1:1 to 4:1. Aluminum zirconium saltcomplexes containing the neutral amino acid glycine are commonlydesignated glycinate salts and are typically abbreviated ZAG forzirconium (Z) aluminum (A) glycinate (G).

It is especially preferred to utilize enhanced efficacy aluminum andaluminum-zirconium antiperspirant salts in the gel sticks of the presentinvention. By "enhanced efficacy antiperspirant salts" is meantantiperspirant salts which, when reconstituted as 10% aqueous solutions,produce an HPLC chromatogram (as described, for example, in U.S. Pat.No. 5,330,751, which is incorporated herein by reference) wherein atleast 70%, preferably at least 80%, of the aluminum is contained in twosuccessive peaks, conveniently labeled peaks 3 and 4, wherein the ratioof the area under peak 4 to the area under peak 3 is at least 0.5,preferably at least 0.7, and most preferably at least 0.9 higher. Anysuitable HPLC technique may be employed provided that it is capable ofresolving the Al component into five peaks. The enhanced efficacy (oractivated) antiperspirant salts are well-known in the industry and arecommercially available from several suppliers.

The antiperspirant salt is dissolved in the liquid vehicle or a portionof the liquid vehicle. The antiperspirant salt is dissolved or dispersedin a liquid vehicle or a portion of the liquid vehicle. The siliconecompositions of the present invention provide a new liquid vehicle forthe dissolution or dispersal of the antiperspirant or deodorant salts.Especially preferred are solubilized salts which have been partiallyneutralized by addition of a pH-raising agent to a pH of about 4.1 to5.0, preferably about 4.3 to 4.8. Particularly preferred neutralizedantiperspirant salts are those which contain an additional alkalineglycinate, such as sodium, potassium, or zinc glycinate. Suchsolubilized antiperspirant salts are described in U.S. Pat. No.5,643,558 entitled Method Of Making Polyhydric Alcohol Solutions OfEnhanced Efficacy Antiperspirant Actives and in U.S. Pat. No. 5,463,098,the disclosures of which are incorporated herein by reference. Anexample of such a solubilized salt, which is partially neutralized withzinc glycinate, is Westchlor A2Z 8106 (Westwood Chemical Corp.). Thepreparation of a preferred solubilized antiperspirant salt is describedin Example 1 below. The additional alkaline glycinate which ispreferably included in the solubilized antiperspirant salt raises the pHof the antiperspirant salt and, as a result, reduces the degradation ofthe dibenzylidene alditol in the gel stick. It is generally preferred toadd sufficient alkaline glycinate to the solubilized antiperspirant saltso as to raise the pH of an approximately 10% aqueous solution of theantiperspirant salt to about 4.1 to 5.0, preferably about 4.3 to 4.8.(The 10% aqueous solution may be an approximately 50:50 polyhydricalcohol:water solution.) Preferred deodorant or antiperspirantcompositions which include such a partially neutralized salt will have apH greater than 4.4, preferably about 4.7 to about 5.5, and morepreferably about 4.8 to about 5.3. The pH of the finished compositioncan be measured by dissolving one part stick in ninety-nine parts water.The pH of the solubilized antiperspirant salt or of the resultingcomposition can, of course, be adjusted to the aforementioned preferredpH ranges with any pH-raising agent, or combination of pH-raisingagents, provided that the agent or agents selected are soluble in thevehicle and do not adversely affect the optical properties or odorcharacteristics of the stick to a significant extent. Sufficientantiperspirant salt should be dissolved in the liquid vehicle so thatthe final composition, after all components are added, includes betweenabout 1% and about 22%, preferably between about 2% and about 15%, ofthe antiperspirant salt by weight. It should be noted that referencethroughout this application to weight percent of antiperspirant salt isintended to be calculated in accordance with the standard industrymethod, which includes bound water and glycine.

All U.S. patents referenced herein are herewith and hereby specificallyincorporated by reference.

Experimental

Functionalized silicones were made by the hydrosilylation of an allylmodified 1,2-diol (mono-allyl glycerine) and 1,3-diol(trimethylolpropane mono allyl ether). The products were functionalizedeither on the backbone or on the termini. The table shows a comparisonof these products contrasting their viscosities, miscibilities with theAP salt solution and relative feel of the product.

    __________________________________________________________________________                              Solubility                                          Product #                                                                          Structure                                                                           Function..sup.1                                                                    % Silicone                                                                         Visc(cSt)                                                                          DPG.sup.2                                                                        ZAG/PG.sup.3                                                                       Feel                                        __________________________________________________________________________    1    MD.sub.4 'M                                                                         1,3-DIOL                                                                           37%       yes                                                                              yes  tacky                                         2 M'D.sub.3 M' 1,3-DIOL 51% 469 yes yes silky                                 3 MD.sub.6.4 D'.sub.5 M 1,3-DIOL 52% 5100 yes yes v.tacky                     4 MD.sub.10 D'.sub.7 M 1,3-DIOL 52% 3700 yes yes v.tacky                      5 M'D.sub.3 M' 1,2-DIOL 57% 515 yes yes v.silky                               6 M'D.sub.5 M' 1,3-DIOL 59% 907  no silky                                     7 MD.sub.6.4 D'.sub.5 M 1,2-DIOL 59% 5480 yes yes v.tacky                     8 MD.sub.3 D'.sub.3 M 1,2-DIOL 59%  yes yes tacky                             9 MD.sub.7 D'.sub.3 M 1,3-DIOL 61% 1050 no no tacky                           10 M'D.sub.5 M' 1,2-DIOL 66% 630 yes yes v.silky                              11 M'D.sub.7.5 M' 1,3-DIOL 66% 746  no silky                                  12 MD.sub.7 D'.sub.3 M 1,2-DIOL 69%  yes no tacky.sup.4                       13 M'D.sub.7.5 M' 1,2-DIOL 72% 502 yes no v.silky                             14 M'D.sub.10 M' 1,3-DIOL 72% 240 no no silky.sup.4                           15 M'D.sub.10 M' 1,2-DIOL 77% 460 yes no v.silky                              16 MD.sub.20 D'.sub.3 M 1,3-DIOL 78%  no no tacky.sup.4                       17 M'D.sub.25 M' 1,2-DIOL 88% 422 no no v.silky                             __________________________________________________________________________     .sup.1 1,3DIOL is TMPMAE and 1,2DIOL is Monoallyl glycerine.                  .sup.2 DPG = dipropylene glycol.                                              .sup.3 ZAG = 28% Zirconiumaluminum glycine salt in propylene glycol.          .sup.4 Product soluble in D.sub.5.                                       

Analyses

Viscosities were measured in Ostwald tube using appropriately-sizedtubes to give flow times of 200-1000 seconds. For the high viscosityfluids (>2000 cPs) the measurements were made on a Brookfield ModelDV-III Programmable Rheometer. The hydrosilylation reactions werefollowed by monitoring the disappearance of the silicon hydrideabsorbance at 2160 cm⁻¹ on a Nicolet 5DXB FTIR Spectrometer. Hydrideanalyses of the starting silicone hydride fluids were performedgasiometrically with sodium t-butoxide in t-butanol as the titrant.Percent solids were measured by heating 1 gram of sample in an aluminumpan in an oven at 150° C. for 45 minutes.

Syntheses

Mono allyl glycerine (MAG) was obtained from FLUKA Chemical Company,Trimethylol propane mono-allyl ether (TMPMAE) was obtained from PerstorpChemical Company and the antiperspirant salt solution from WestwoodChemical Company.

1,3-DIOL-functionalized Silicone Syntheses(Product #3)

A 3 liter flask was charged with TMPMAE (918.4 g, 5.34 mol) andcyclohexane (526.0 g). The flask was equipped with a dean stark trap, acondenser, a thermometer, a stir bar and a nitrogen sparge. The mixturewas heated to reflux temperature which was about 90° C., toazeotropically dry the reaction. The reactor was cooled to 80° C. and0.23 g of Karstedt's catalyst was added to the mixture. An additionfunnel was charged with the hydride (MD₆.4 D^(H) ₅ M, 492.6 g, 2.63 molSiH) which was slowly added over a 2 hour period to control theexotherm. The reaction was stirred at 90° C. for an additional 2-3 hourswhile following hydride loss by FTIR. The reaction was stripped for 3hours with full vacuum at 130° C. until reaching 90% solids. The finalviscosity was 5100 cPs and the refractive index (RI) was 1.4549.

1,2-DIOL--functionalized Silicone Synthesis: (Product #13)

A 500 ml flask was charged with MAG (76.66 g, 0.58 moles), cyclohexane(74.54 g), and Karstedt's catalyst (34.3 mg) was added. The mixture washeated to 85° C. An addition funnel was charged with the hydride fluid(M^(H) D₇.5 M^(H), 100.03 g, 0.29 mol SiH). The hydride fluid was addedover a 45 minute period and the temperature was maintained at 85° C. fortwo additional hours. The reaction was tested by FTIR for completion.Solvent was stripped out with a vacuum pump at 130° C. with a nitrogensparge for five hours. The product had a final solids of 99%, viscositywas 502 cSt and RI was 1.430.

Clear AP Stick Formulation #1

To a 2 oz jar was added Product #7 (20.04 g) and dibenzylidene sorbitol,DBS, (0.83 g) was added gingerly. The mixture was heated to 190° C.before the DBS dissolved. The heated mixture was cooled to 135° C. andadded to a heated (50° C.) solution of 28% ZAG salt in propylene glycol(20 g). A solid stick was produced which felt tacky on the forearm.

Clear AP Stick Formulation #2

To a 2 oz jar was added Product #5 (98 g) and dibenzylidene sorbitol,DBS, (2.00 g) was added gingerly. The mixture was heated to 170° C.before the DBS dissolved. The heated mixture was cooled to 135° C. andadded to a heated (50° C.) solution of 28% ZAG salt propylene glycol(100 g). A solid stick was produced which felt smooth and dry bycomparison when tested on the forearm.

Having described the invention that which is claimed is:
 1. A siliconecompound having the formula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,subject to the limitation that the sum of the subscripts b, d and f isone or greater; where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂CH₂ -- and the subscript h is 1, 2 or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂CH₂ -- and the subscript i is 1 or 2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formulaSiO_(4/2).
 2. The compound of claim 1 wherein g is zero.
 3. The compoundof claim 2 wherein f is zero.
 4. The compound of claim 3 wherein e iszero.
 5. The compound of claim 4 wherein d is zero.
 6. The compound ofclaim 4 wherein c is zero.
 7. The compound of claim 4 wherein b is zero.8. The compound of claim 4 wherein a is zero.
 9. The compound of claim 5wherein c ranges from 3 to
 25. 10. The compound of claim 6 wherein dranges from 3 to
 25. 11. A mixture of silicone compounds comprising asilicone compound having the formula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,subject to the limitation that the sum of the subscripts b, d and f isone or greater; where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂CH₂ -- and the subscript h is 1, 2 or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂CH₂ -- and the subscript i is 1 or 2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formulaSiO_(4/2).
 12. The compound of claim 11 wherein g is zero.
 13. Thecompound of claim 12 wherein f is zero.
 14. The compound of claim 13wherein e is zero.
 15. The compound of claim 14 wherein d is zero. 16.The compound of claim 14 wherein c is zero.
 17. The compound of claim 14wherein b is zero.
 18. The compound of claim 14 wherein a is zero. 19.The compound of claim 15 wherein c ranges from 3 to
 25. 20. The compoundof claim 16 wherein d ranges from 3 to
 25. 21. A silicone compoundhaving the formula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,the subscript b is a positive integer of 2 or greater and the subscriptc is a positive integer of 1 or greater; where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript h is 1, 2or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript i is 1 or2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is a monovalent hydrocarbon radical selected from the groupconsisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ -- and (HOCH₂)₂ C(CH₂CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formula SiO_(4/2).
 22. A personalcare composition comprising the compound of claim 1 and furthercomprising a salt of aluminum or zirconium.
 23. A personal carecomposition comprising the compound of claim 9 and further comprising asalt of aluminum or zirconium.
 24. A personal care compositioncomprising the compound of claim 10 and further comprising a salt ofaluminum or zirconium.
 25. A personal care composition comprising: asilicone compound having the formula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, c, d, e, f and g are zero or a positive integer,subject to the limitation that the sum of the subscripts b, d and f isone or greater; where M has the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript h is 1, 2or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript i is 1 or2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is a monovalent hydrocarbon radical selected from the groupconsisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ -- and (HOCH₂)₂ C(CH₂CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formula SiO_(4/2) ; and a salt ofaluminum or zirconium.
 26. A personal care composition comprising: asilicone compound having the formula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, b and c are a positive integer, the subscriptsd, e, f and g are zero, and the subscript c ranges from 3 to 25; where Mhas the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript h is 1, 2or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript i is 1 or2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is a monovalent hydrocarbon radical selected from the groupconsisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ -- and (HOCH₂)₂ C(CH₂CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formula SiO_(4/2) ; and a salt ofaluminum or zirconium.
 27. A personal care composition comprising: asilicone compound having the formula:

    M.sub.a M'.sub.b D.sub.c D'.sub.d T.sub.e T'.sub.f Q.sub.g

where the subscripts a, b and d are a positive integer, the subscriptsc, e, f and g are zero, and the subscript c ranges from 3 to 25; where Mhas the formula:

    R.sup.1.sub.3 SiO.sub.1/2,

where each R¹ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; M' has the formula:

    R.sup.2.sub.3-h R.sup.3.sub.h SiO.sub.1/2,

where each R² is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R³ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript h is 1, 2or 3; D has the formula:

    R.sup.4.sub.2 SiO.sub.2/2,

where each R⁴ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms; D' has the formula:

    R.sup.5.sub.2-i R.sup.6.sub.i SiO.sub.2/2

where each R⁶ is independently a monovalent hydrocarbon radical havingfrom one to forty carbon atoms, R⁵ is a monovalent hydrocarbon radicalselected from the group consisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ --and (HOCH₂)₂ C(CH₂ CH₃)CH₂ OCH₂ CH₂ CH₂ -- and the subscript i is 1 or2; T has the formula:

    R.sup.7 SiO.sub.3/2,

where each R⁷ is a monovalent hydrocarbon radical having from one toforty carbon atoms; T' has the formula:

    R.sup.8 SiO.sub.3/2,

where R⁸ is a monovalent hydrocarbon radical selected from the groupconsisting of H₂ (OH)CCH(OH)CH₂ OCH₂ CH₂ CH₂ -- and (HOCH₂)₂ C(CH₂CH₃)CH₂ OCH₂ CH₂ CH₂ -- and Q has the formula SiO_(4/2) ; and a salt ofaluminum or zirconium.